CN105461966A - Multifunctional degradable humic acid liquid mulching film - Google Patents

本发明公开了一种多功能可降解腐殖酸液态地膜，按照质量份包括以下组分：改性纤维素5份-20份，煤0.01份-10份，水40份-80份，成膜剂5份-10份，交联剂3份-10份，表面活性剂0.001份-1份，引发剂0.01份-1份，化肥0份-2份，除草剂0份-1份。本发明还公开了一种多功能可降解腐殖酸液态地膜的制备方法，采用本方法制备得到的多功能可降解腐殖酸液态地膜，使用方便，喷洒后即可在土壤表面形成膜结构，强度接近普通塑料地膜，能起到很好的覆盖作用，而且具有一般光降解和生物降解的作用，在使用后可以完全降解，避免了白色污染，还能为土壤提供有机肥和无机肥。The invention discloses a multifunctional and degradable humic acid liquid film, which comprises the following components in parts by mass: 5-20 parts of modified cellulose, 0.01-10 parts of coal, 40-80 parts of water, and film-forming 5-10 parts of agent, 3-10 parts of cross-linking agent, 0.001-1 part of surfactant, 0.01-1 part of initiator, 0-2 parts of chemical fertilizer, 0-1 part of herbicide. The invention also discloses a method for preparing a multifunctional degradable humic acid liquid mulch film. The multifunctional degradable humic acid liquid mulch film prepared by the method is easy to use and can form a film structure on the soil surface after spraying. The strength is close to that of ordinary plastic mulch, which can play a good covering role, and has general photodegradation and biodegradation effects. It can be completely degraded after use, avoiding white pollution, and can also provide organic and inorganic fertilizers for the soil.

一种多功能可降解腐殖酸液态地膜A multifunctional and degradable humic acid liquid mulch film

技术领域technical field

本发明属于农用地膜技术领域，具体涉及一种多功能可降解腐殖酸液态地膜。The invention belongs to the technical field of agricultural mulch, and in particular relates to a multifunctional and degradable humic acid liquid mulch.

背景技术Background technique

农用塑料地膜覆盖技术的广泛应用，对提高农作物产量起到了重要作用。然而塑料地膜的降解时间长达200-300年，长期使用给生态环境造成了严重的“白色污染”。因此，关于可降解地膜的研究引起了人们的极大兴趣，开发出了各种各样的可降解地膜，按其形态可分为固体地膜和液体地膜。固体地膜相对普通塑料地膜较厚，价格较高，绝大多数还难以完全降解，其应用受到一定限制。液态地膜由于其降解性能好，已有开发和试用。如中国专利CN1209443提到的喷洒隐性地膜是羟基氯丁醇胶乳树脂溶液，喷洒时由于无色无法控制成膜质量，且成本较高，未见投入实际使用。中国专利CN1459471A提到的多功能可降解黑色液态地膜，喷洒后，在地表形成油状薄膜，但膜的强度较低，实际效果不好。The wide application of agricultural plastic mulching technology has played an important role in improving crop yields. However, the degradation time of plastic mulch is as long as 200-300 years, and long-term use has caused serious "white pollution" to the ecological environment. Therefore, the research on degradable mulch has aroused great interest, and various degradable mulches have been developed, which can be divided into solid mulch and liquid mulch according to their morphology. Compared with ordinary plastic mulches, solid mulches are thicker and more expensive, and most of them are difficult to completely degrade, so their applications are limited. Liquid mulch has been developed and tested due to its good degradation performance. As mentioned in Chinese patent CN1209443, the sprayed invisible mulch film is a hydroxychlorobutanol latex resin solution, which cannot be controlled due to the colorless film quality during spraying, and the cost is relatively high, so it has not been put into practical use. Chinese patent CN1459471A mentions the multifunctional degradable black liquid mulch film, after spraying, forms an oily film on the ground surface, but the strength of the film is low, and the actual effect is not good.

发明内容Contents of the invention

本发明的目的是提供一种多功能可降解腐殖酸液态地膜，解决了现有液态地膜技术中存在的成本较高、来源受限、实用性差的问题。The purpose of the present invention is to provide a multifunctional and degradable humic acid liquid mulch, which solves the problems of high cost, limited source and poor practicability existing in the existing liquid mulch technology.

本发明的另一目的是提供一种多功能可降解腐殖酸液态地膜的制备方法。Another object of the present invention is to provide a method for preparing a multifunctional degradable humic acid liquid mulch film.

本发明所采用的第一技术方案是，一种多功能可降解腐殖酸液态地膜，按照质量份包括以下组分：改性纤维素5份-20份，煤0.01份-10份，水40份-80份，成膜剂5份-10份，交联剂3份-10份，表面活性剂0.001份-1份，引发剂0.01份-1份，化肥0份-2份，除草剂0份-1份。The first technical solution adopted in the present invention is a multifunctional degradable humic acid liquid mulch film, which includes the following components in parts by mass: 5-20 parts of modified cellulose, 0.01-10 parts of coal, 40 parts of water Parts - 80 parts, film forming agent 5 parts - 10 parts, crosslinking agent 3 parts - 10 parts, surfactant 0.001 parts - 1 part, initiator 0.01 parts - 1 part, fertilizer 0 parts - 2 parts, herbicide 0 parts Servings - 1 serving.

进一步地，成膜剂为乙二醇、丙三醇、改性纤维素中的一种或多种的混合物。Further, the film forming agent is a mixture of one or more of ethylene glycol, glycerol, and modified cellulose.

进一步地，煤为褐煤、风化煤以及它们氧化、硝化产物中的一种或多种的混合物。Further, the coal is a mixture of one or more of lignite, weathered coal and their oxidation and nitration products.

进一步地，改性纤维素是羧甲基纤维素、羧乙基纤维素和羟丙基纤维素中的一种或多种的混物。Further, the modified cellulose is a mixture of one or more of carboxymethyl cellulose, carboxyethyl cellulose and hydroxypropyl cellulose.

进一步地，表面活性剂为十二烷基硫酸钠、十六烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种的混合物。Further, the surfactant is a mixture of one or more of sodium lauryl sulfate, sodium cetyl sulfate, and sodium dodecylbenzenesulfonate.

进一步地，交联剂为三乙醇胺或六甲氧基三聚氰胺；所述引发剂为对甲基苯磺酸；所述化肥为施可丰缓释肥。Further, the crosslinking agent is triethanolamine or hexamethoxymelamine; the initiator is p-toluenesulfonic acid; and the fertilizer is Shikefeng slow-release fertilizer.

本发明所采用的第二技术方案是，一种多功能可降解腐殖酸液态地膜的制备方法，包括以下步骤：The second technical scheme adopted in the present invention is a preparation method of a multifunctional degradable humic acid liquid mulch film, comprising the following steps:

1)称量：按照质量份称量以下组分：改性纤维素5份-20份，煤0.01份-10份，水40份-80份，成膜剂5份-10份，交联剂3份-10份，表面活性剂0.001份-1份，引发剂0.01份-1份，化肥0份-2份，除草剂0份-1份；1) Weighing: Weigh the following components in parts by mass: 5-20 parts of modified cellulose, 0.01-10 parts of coal, 40-80 parts of water, 5-10 parts of film-forming agent, and cross-linking agent 3-10 parts, 0.001-1 part of surfactant, 0.01-1 part of initiator, 0-2 parts of chemical fertilizer, 0-1 part of herbicide;

2)将成称量好的煤粉碎至50-300目，用酸处理30分钟，用碱中和，然后用焦磷酸钠碱液水浴抽提1-3个小时，冷却过滤，过滤液中和至中性，取上层清液，得到腐殖酸溶液；2) Crush the weighed coal to 50-300 mesh, treat with acid for 30 minutes, neutralize with alkali, then extract with sodium pyrophosphate lye in water bath for 1-3 hours, cool and filter, and neutralize the filtrate until Neutral, take the supernatant to obtain humic acid solution;

3)用上层清液溶解的改性纤维素，于50-80℃糊化30-40分钟；3) The modified cellulose dissolved in the supernatant liquid is gelatinized at 50-80° C. for 30-40 minutes;

4)依次加入交联剂、成膜剂和引发剂；所得溶液在90-150℃下搅拌聚合1-3个小时；4) adding a crosslinking agent, a film forming agent and an initiator in sequence; the resulting solution is stirred and polymerized at 90-150° C. for 1-3 hours;

5)在步骤4)中的聚合液中加入表面活性剂、化肥和除草剂，得到多功能可降解腐殖酸液态地膜。5) Add surfactants, chemical fertilizers and herbicides to the polymerization solution in step 4) to obtain a multifunctional and degradable humic acid liquid mulch film.

进一步地，步骤2)中的酸为质量浓度为30％的硝酸。Further, the acid in step 2) is nitric acid with a mass concentration of 30%.

进一步地，步骤2)中的碱为质量浓度为50％的氢氧化钠。Further, the alkali in step 2) is sodium hydroxide with a mass concentration of 50%.

进一步地，焦磷酸钠碱液为将15g结晶Na₄P₂O₇.10H₂O和10g氢氧化钠溶于1000mL水中，其浓度为2.15％。Further, the sodium pyrophosphate lye is 15g of crystalline Na ₄ P ₂ O ₇ .10H ₂ O and 10g of sodium hydroxide dissolved in 1000mL of water, and its concentration is 2.15%.

本发明的有益效果是：The beneficial effects of the present invention are:

本发明通过选择特定类型交联剂和配比优化，达到控制交联强度目的。获得适宜的交联强度、既满足地膜保苗保墒的短期作用(40天左右)，又能在使用后较快降解。The invention achieves the purpose of controlling the cross-linking strength by selecting a specific type of cross-linking agent and optimizing the ratio. Obtaining a suitable cross-linking strength not only satisfies the short-term effect (about 40 days) of mulching to protect seedlings and moisture, but also degrades quickly after use.

交联剂选择三乙醇胺或六甲氧基三聚氰胺，制备得到的多功能可降解腐殖酸液态地膜在土壤中具有不错的降解性能。埋在土壤中6周后，其重量损失达到67.83％，此时已经不能测定其抗张强度。7周容易碎裂成小块分散在土壤中。The crosslinking agent is triethanolamine or hexamethoxymelamine, and the prepared multifunctional degradable humic acid liquid mulch film has good degradation performance in soil. After being buried in the soil for 6 weeks, its weight loss reached 67.83%, and its tensile strength could not be measured at this time. 7 weeks It is easy to break into small pieces and disperse in the soil.

1.使用方便，喷洒后即可在土壤表面形成膜结构，强度接近普通塑料地膜，能起到很好的覆盖作用，而且具有一般光降解和生物降解的作用，在使用后可以完全降解，避免了白色污染，还能为土壤提供有机肥和无机肥。1. It is easy to use. After spraying, it can form a film structure on the soil surface. The strength is close to that of ordinary plastic mulch, and it can play a good covering role. It also has general photodegradation and biodegradation effects. It can be completely degraded after use, avoiding In addition to white pollution, it can also provide organic and inorganic fertilizers for the soil.

2.采用改性纤维素和廉价的煤为原料，大大降低了可降解地膜的生产成本，提高了地膜的吸热保墒性能，合理利用了资源，具有很好的市场前景。2. The use of modified cellulose and cheap coal as raw materials greatly reduces the production cost of degradable plastic film, improves the heat-absorbing and moisture-retaining performance of the plastic film, and makes rational use of resources, which has a good market prospect.

3.本发明所得的产品浓度高，便于储存运输。3. The product obtained by the present invention has high concentration and is convenient for storage and transportation.

具体实施方式detailed description

下面结合具体实施方式对本发明进行详细说明。The present invention will be described in detail below in combination with specific embodiments.

本发明提供一种多功能可降解腐殖酸液态地膜，按照质量份包括以下组分：改性纤维素5份-20份，煤0.01份-10份，水40份-80份，成膜剂5份-10份，交联剂3份-10份，表面活性剂0.001份-1份，引发剂0.01份-1份，化肥0份-2份，除草剂0份-1份。The invention provides a multifunctional and degradable humic acid liquid film, which comprises the following components in parts by mass: 5-20 parts of modified cellulose, 0.01-10 parts of coal, 40-80 parts of water, and a film-forming agent 5-10 parts, 3-10 parts of cross-linking agent, 0.001-1 part of surfactant, 0.01-1 part of initiator, 0-2 parts of chemical fertilizer, 0-1 part of herbicide.

其中，成膜剂为乙二醇、丙三醇、改性纤维素中的一种或多种的混合物。煤为褐煤、风化煤以及它们氧化、硝化产物中的一种或多种的混合物。改性纤维素是羧甲基纤维素、羧乙基纤维素和羟丙基纤维素中的一种或多种的混物。表面活性剂为十二烷基硫酸钠、十六烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种的混合物。交联剂为三乙醇胺或六甲氧基三聚氰胺；所述引发剂为对甲基苯磺酸；所述化肥为施可丰缓释肥。所述除草剂为草甘膦、巨星、禾大壮等非正离子型活性基除草剂中的一种。Wherein, the film-forming agent is one or more mixtures of ethylene glycol, glycerol, and modified cellulose. Coal is one or more mixtures of lignite, weathered coal and their oxidation and nitrification products. Modified cellulose is a mixture of one or more of carboxymethyl cellulose, carboxyethyl cellulose and hydroxypropyl cellulose. The surfactant is one or more mixtures of sodium lauryl sulfate, sodium cetyl sulfate and sodium dodecylbenzenesulfonate. The cross-linking agent is triethanolamine or hexamethoxymelamine; the initiator is p-toluenesulfonic acid; and the chemical fertilizer is Shi Kefeng slow-release fertilizer. The herbicide is one of non-positive ion active group herbicides such as glyphosate, giant star, and Croda Zhuang.

增塑剂(成膜剂)以甘油(丙三醇)和山梨醇效果比较好，乙二醇的效果比较差。主要原因是因为乙二醇分子结构中含有的羟基少，结合的水分子就比较少，成膜脆，质地比较硬，抗张强度较低。山梨醇是六元醇，甘油是三元醇，结合水分较多，地膜性能比较好，但是二者抗张强度差异比较显著。由于山梨醇的成本比甘油高，综合各种考虑，最终确定最佳的增塑剂是甘油(丙三醇)。As plasticizer (film former), glycerin (glycerol) and sorbitol are more effective, and ethylene glycol is less effective. The main reason is that because the molecular structure of ethylene glycol contains less hydroxyl groups, the combined water molecules are less, the film is brittle, the texture is relatively hard, and the tensile strength is low. Sorbitol is a hexavalent alcohol, and glycerin is a trihydric alcohol, which has more combined water and better film performance, but there is a significant difference in tensile strength between the two. Since the cost of sorbitol is higher than that of glycerin, considering various considerations, it is finally determined that the best plasticizer is glycerin (glycerol).

当甘油(丙三醇)的质量分数超过5.0％时，形成的膜质地就非常柔软，并且会有少量甘油析出，数据不容易测出来；当甘油质量分数低于2.0％时，成膜就比较脆，容易发生断裂，其原因是结合的水份较少。当甘油的质量分数在2.0％～5.0％之间时，能够得到具有一定弹性的地膜。When the mass fraction of glycerol (glycerol) exceeds 5.0%, the film texture that forms is just very soft, and there will be a small amount of glycerin to separate out, and the data is not easy to measure; Brittle and prone to breakage, the reason is that there is less water combined. When the mass fraction of glycerin is between 2.0% and 5.0%, a film with certain elasticity can be obtained.

本发明还提供一种多功能可降解腐殖酸液态地膜的制备方法，包括以下步骤：The present invention also provides a method for preparing a multifunctional degradable humic acid liquid film, comprising the following steps:

1)称量：按照质量份称量以下组分：改性纤维素5份-20份，煤0.01份-10份，水40份-80份，成膜剂5份-10份，交联剂3份-10份，表面活性剂0.001份-1份，引发剂0.01份-1份，化肥0份-2份，除草剂0份-1份；1) Weighing: Weigh the following components in parts by mass: 5-20 parts of modified cellulose, 0.01-10 parts of coal, 40-80 parts of water, 5-10 parts of film-forming agent, and cross-linking agent 3-10 parts, 0.001-1 part of surfactant, 0.01-1 part of initiator, 0-2 parts of chemical fertilizer, 0-1 part of herbicide;

2)将成称量好的煤粉碎至50-300目，用酸处理30分钟，用碱中和，然后用焦磷酸钠碱液水浴抽提1-3个小时，冷却过滤，过滤液中和至中性，取上层清液；其中，酸为质量浓度为30％的硝酸；碱为质量浓度为50％的氢氧化钠；焦磷酸钠碱液为将15g结晶Na₄P₂O₇.10H₂O和10g氢氧化钠溶于1000mL水中，其浓度为2.15％。2) Crush the weighed coal to 50-300 mesh, treat with acid for 30 minutes, neutralize with alkali, then extract with sodium pyrophosphate lye in water bath for 1-3 hours, cool and filter, and neutralize the filtrate until Neutral, take the supernatant; Wherein, the acid is nitric _acid with a mass concentration of ₃₀ %; the alkali is _sodium hydroxide with a mass concentration of 50% _; O and 10g of sodium hydroxide are dissolved in 1000mL of water, and its concentration is 2.15%.

3)用上层清液溶解的改性纤维素，于50-80℃糊化30-40分钟；3) The modified cellulose dissolved in the supernatant liquid is gelatinized at 50-80° C. for 30-40 minutes;

4)依次加入交联剂、成膜剂和引发剂；所得溶液在90-150℃下搅拌聚合1-3个小时；4) adding a crosslinking agent, a film forming agent and an initiator in sequence; the resulting solution is stirred and polymerized at 90-150° C. for 1-3 hours;

5)在步骤4)中的聚合液中加入表面活性剂、化肥和除草剂，得到多功能可降解腐殖酸液态地膜。5) Add surfactants, chemical fertilizers and herbicides to the polymerization solution in step 4) to obtain a multifunctional and degradable humic acid liquid mulch film.

实施例1Example 1

1)将2克研磨至200目的褐煤，用30％的硝酸溶液将其氧化30分钟后，用氢氧化钠中和，再用焦磷酸钠碱液抽提2小时，过滤后清液用盐酸中和，蒸发浓缩得到腐殖酸溶液60mL。1) Grind 2 grams of lignite to 200 mesh, oxidize it with 30% nitric acid solution for 30 minutes, neutralize it with sodium hydroxide, extract it with sodium pyrophosphate lye for 2 hours, and neutralize the clear liquid with hydrochloric acid after filtration And, evaporate and concentrate to obtain humic acid solution 60mL.

2)将5克羧甲基纤维素分散到腐殖酸溶液中，在60℃条件下搅拌糊化30分钟，然后加入六甲氧基三聚氰胺4克，丙三醇3mL，对甲苯磺酸1克，十二烷基硫酸钠0.3克，所得溶液于130℃下搅拌聚合1小时，最后加入化肥0.1克，除草剂0.01克，得本发明多功能可降解腐殖酸液态地膜。2) Disperse 5 grams of carboxymethylcellulose into the humic acid solution, stir and gelatinize at 60°C for 30 minutes, then add 4 grams of hexamethoxymelamine, 3 mL of glycerin, and 1 gram of p-toluenesulfonic acid, 0.3 g of sodium lauryl sulfate, the resulting solution was stirred and polymerized at 130° C. for 1 hour, and finally 0.1 g of chemical fertilizer and 0.01 g of herbicide were added to obtain the multifunctional degradable humic acid liquid mulch film of the present invention.

实施例2Example 2

1)将3克研磨至150目的褐煤，用35％的硝酸溶液将其氧化30分钟后，用氢氧化钠中和，再用焦磷酸钠碱液抽提2小时，过滤后清液用盐酸中和，蒸发浓缩得到腐殖酸溶液65mL。1) Grind 3 grams of lignite to 150 mesh, oxidize it with 35% nitric acid solution for 30 minutes, neutralize it with sodium hydroxide, extract it with sodium pyrophosphate lye for 2 hours, and neutralize the clear liquid with hydrochloric acid after filtration And, evaporate and concentrate to obtain humic acid solution 65mL.

2)将6克羟丙基纤维素分散到腐植酸溶液中，在70℃条件下搅拌糊化40分钟，然后加入六甲氧基三聚氰胺4.5克，丙三醇3mL，对甲苯磺酸1克，十六烷基硫酸钠0.3克，所得溶液于120℃下搅拌聚合1小时，最后加入化肥0.15克，得本发明多功能可降解腐殖酸液态地膜。2) Disperse 6 grams of hydroxypropyl cellulose into the humic acid solution, stir and gelatinize at 70°C for 40 minutes, then add 4.5 grams of hexamethoxymelamine, 3 mL of glycerol, 1 gram of p-toluenesulfonic acid, ten 0.3 g of sodium hexaalkyl sulfate, the resulting solution was stirred and polymerized at 120° C. for 1 hour, and finally 0.15 g of chemical fertilizer was added to obtain the multifunctional degradable humic acid liquid mulching film of the present invention.

实施例3Example 3

1)将3克研磨至200目的风化煤，用40％的硝酸溶液将其氧化40分钟后，用氢氧化钠中和，再用焦磷酸钠碱液抽提1.5小时，过滤后清液用盐酸中和，蒸发浓缩得到腐殖酸溶液60mL。1) Grind 3 grams of weathered coal to 200 mesh, oxidize it with 40% nitric acid solution for 40 minutes, neutralize it with sodium hydroxide, extract it with sodium pyrophosphate lye for 1.5 hours, filter the clear liquid with hydrochloric acid Neutralize, evaporate and concentrate to obtain 60 mL of humic acid solution.

2)将8克羧甲基纤维素分散到腐植酸溶液中，在65℃条件下搅拌糊化45分钟，然后加入乙二醇3mL，三乙醇胺3mL，过硫酸钾1.5克，十二烷基硫酸钠0.2克，所得溶液于130℃下搅拌聚合1.5小时，最后加入除草剂0.01克，得本发明多功能可降解腐殖酸液态地膜。2) Disperse 8 grams of carboxymethyl cellulose into the humic acid solution, stir and gelatinize at 65°C for 45 minutes, then add 3 mL of ethylene glycol, 3 mL of triethanolamine, 1.5 grams of potassium persulfate, and lauryl sulfate 0.2 g of sodium, the resulting solution was stirred and polymerized at 130° C. for 1.5 hours, and finally 0.01 g of herbicide was added to obtain the multifunctional degradable humic acid liquid mulching film of the present invention.

实施例4Example 4

1)将1千克研磨至250目的风化煤，用35％的硝酸溶液将其氧化35分钟后，用氢氧化钠中和，再用焦磷酸钠碱液抽提2小时，过滤后清液用盐酸中和，蒸发浓缩得到腐殖酸溶液2.8L。1) Grind 1 kg of weathered coal to 250 mesh, oxidize it with 35% nitric acid solution for 35 minutes, neutralize it with sodium hydroxide, extract it with sodium pyrophosphate lye for 2 hours, filter the clear liquid with hydrochloric acid Neutralize, evaporate and concentrate to obtain 2.8 L of humic acid solution.

2)将2.8千克羟乙基纤维素分散到腐植酸溶液中，在65℃条件下搅拌糊化40分钟，然后加入六甲氧基三聚氰胺0.8千克，乙二醇1.2L，对甲苯磺酸0.6千克，十二烷基苯磺酸钠0.8千克，所得溶液于120℃下搅拌聚合2小时，最后加入化肥0.05千克，除草剂0.004千克，得本发明多功能可降解腐殖酸液态地膜。2) Disperse 2.8 kg of hydroxyethyl cellulose into the humic acid solution, stir and gelatinize at 65°C for 40 minutes, then add 0.8 kg of hexamethoxymelamine, 1.2 L of ethylene glycol, and 0.6 kg of p-toluenesulfonic acid, 0.8 kg of sodium dodecylbenzenesulfonate, the resulting solution was stirred and polymerized at 120°C for 2 hours, and finally 0.05 kg of chemical fertilizer and 0.004 kg of herbicide were added to obtain the multifunctional degradable humic acid liquid mulch film of the present invention.

实施例5Example 5

一种多功能可降解腐殖酸液态地膜的制备方法，包括以下步骤：A preparation method of a multifunctional degradable humic acid liquid mulch film, comprising the following steps:

1)称量：按照质量份称量以下组分：羟丙基纤维素5份，风化煤10份，水40份，丙三醇10份，六甲氧基三聚氰胺3份，十二烷基苯磺酸钠1份，对甲基苯磺酸0.01份，施可丰缓释肥2份，除草剂1份；1) Weighing: Weigh the following components in parts by mass: 5 parts of hydroxypropyl cellulose, 10 parts of weathered coal, 40 parts of water, 10 parts of glycerol, 3 parts of hexamethoxymelamine, dodecylbenzenesulfonate 1 part of sodium bicarbonate, 0.01 part of p-toluenesulfonic acid, 2 parts of Shi Kefeng slow-release fertilizer, 1 part of herbicide;

2)将成称量好的风化煤粉碎至50目，用酸处理30分钟，用碱中和，然后用焦磷酸钠碱液水浴抽提1个小时，冷却过滤，过滤液中和至中性，取上层清液；2) Pulverize the weighed weathered coal to 50 mesh, treat with acid for 30 minutes, neutralize with alkali, then extract with sodium pyrophosphate lye water bath for 1 hour, cool and filter, and neutralize the filtrate until neutral. Take the supernatant;

3)用上层清液溶解的羟丙基纤维素，于50℃糊化30分钟；3) Use the hydroxypropyl cellulose dissolved in the supernatant to gelatinize at 50°C for 30 minutes;

4)依次加入六甲氧基三聚氰胺、丙三醇和对甲基苯磺酸；所得溶液在150℃下搅拌聚合3个小时；4) adding hexamethoxymelamine, glycerin and p-toluenesulfonic acid in sequence; the resulting solution was stirred and polymerized at 150° C. for 3 hours;

5)在步骤4)中的聚合液中加入十二烷基苯磺酸钠、化肥除草剂，得到多功能可降解腐殖酸液态地膜。5) Sodium dodecylbenzenesulfonate and chemical fertilizer and herbicide are added to the polymerization solution in step 4) to obtain a multifunctional and degradable humic acid liquid mulch film.

实施例6Example 6

一种多功能可降解腐殖酸液态地膜的制备方法，包括以下步骤：A preparation method of a multifunctional degradable humic acid liquid mulch film, comprising the following steps:

1)称量：按照质量份称量以下组分：羧乙基纤维素20份，褐煤0.01份，水80份，乙二醇5份，三乙醇胺10份，十六烷基硫酸钠0.001份，对甲基苯磺酸1份，施可丰缓释肥0份，草甘膦0份；1) Weighing: Weigh the following components according to parts by mass: 20 parts of carboxyethyl cellulose, 0.01 part of lignite, 80 parts of water, 5 parts of ethylene glycol, 10 parts of triethanolamine, 0.001 part of sodium cetyl sulfate, 1 part of p-toluenesulfonic acid, 0 part of Shi Kefeng slow-release fertilizer, 0 part of glyphosate;

2)将成称量好的煤粉碎至300目，用酸处理30分钟，用碱中和，然后用焦磷酸钠碱液水浴抽提3个小时，冷却过滤，过滤液中和至中性，取上层清液；2) Pulverize the weighed coal to 300 mesh, treat with acid for 30 minutes, neutralize with alkali, then extract with sodium pyrophosphate lye water bath for 3 hours, cool and filter, neutralize the filtrate to neutral, take supernatant;

3)用上层清液溶解的羧乙基纤维素，于80℃糊化40分钟；3) Carboxyethyl cellulose dissolved in the supernatant was gelatinized at 80°C for 40 minutes;

4)依次加入三乙醇胺、乙二醇和对甲基苯磺酸；所得溶液在90℃下搅拌聚合1个小时；4) adding triethanolamine, ethylene glycol and p-toluenesulfonic acid in sequence; the resulting solution was stirred and polymerized at 90° C. for 1 hour;

5)在步骤4)中的聚合液中加入十六烷基硫酸钠、施可丰缓释肥、草甘膦，得到多功能可降解腐殖酸液态地膜。5) Add cetyl sodium sulfate, Shikefeng slow-release fertilizer, and glyphosate to the polymerization solution in step 4) to obtain a multifunctional degradable humic acid liquid mulch film.

实施例1的产品在玉米地地面用温水稀释3倍，然后喷洒成膜。该膜30天开裂，90天完全降解。The product of embodiment 1 is diluted 3 times with warm water on the ground of corn field, then sprays film-forming. The film cracked in 30 days and completely degraded in 90 days.

实施例2的产品在玉米地地面用温水稀释2.5倍，然后喷洒成膜。该膜40天开裂，100天完全降解。The product of embodiment 2 is diluted 2.5 times with warm water on the ground of corn field, then sprays film-forming. The film cracked in 40 days and completely degraded in 100 days.

实施例3的产品在花生地地面用温水稀释1.5倍，然后喷洒成膜。该膜50天开裂，120天完全降解。The product of embodiment 3 is diluted 1.5 times with warm water on the peanut ground, then sprays film-forming. The film cracked in 50 days and completely degraded in 120 days.

实施例4的产品在花生地地面用温水稀释2倍，然后喷洒成膜。该膜45天开裂，110天完全降解。The product of embodiment 4 is diluted 2 times with warm water on the ground of peanut field, then sprays film-forming. The film cracked in 45 days and completely degraded in 110 days.

实施例5的产品在花生地地面用温水稀释1.5倍，然后喷洒成膜。该膜40天开裂，115天完全降解。The product of embodiment 5 is diluted 1.5 times with warm water on the peanut ground, then sprays film-forming. The film cracked in 40 days and completely degraded in 115 days.

实施例6的产品在花生地地面用温水稀释1.8倍，然后喷洒成膜。该膜42天开裂，105天完全降解。The product of embodiment 6 is diluted 1.8 times with warm water on the peanut ground, and then sprayed to form a film. The film cracked in 42 days and completely degraded in 105 days.